Inorganic Chemistry Communications (v.11, #2)

Contents List (iii-viii).

A novel 3D supramolecular inorganic–metal–organic architecture with honeycomb-like motifs directed by the water tetramer and sulfate anion by Hong Wang; Jian-Qiang Liu; Ya-Nan Zhang; Yao-Yu Wang; Gui-Lin Wen; Chun-Yan Guo; Qi-Zhen Shi (129-133).
An interesting 3D supramolecular inorganic–metal–organic architecture was obtained from the 2D inorganic water-sulfate cluster and 1D metal–organic chain. The structure reported herein demonstrates that water-sulfate clusters play the central role of a structure-directing unit.Rectangle-like tetrameric water clusters associate with sulfate anions and coordinated water molecules into a 2D honeycomb-like layer via hydrogen-bonded interactions. The 2D layer acts as “host” supporting the metal–organic “guest” into a 3D supramolecular architecture.
Keywords: Water tetramer; Nickel(II) complex; Sulfate anion; Inorganic–metal–organic architecture; TGA property;

Coexistence of two aromatic bicarboxylate ligands with distinct conformations in a fluorescent zinc(II) polymer by Pei-Xiu Yin; Jian Zhang; Zhao-Ji Li; Ye-Yan Qin; Jian-Kai Cheng; Yuan-Gen Yao (134-137).
A new zinc compound, [Zn3(DPA)2(BDC)] n (1, H2DPA = diphenic acid and H2BDC = benzene-1,4-dicarboxylic acid), has been hydrothermally prepared and characterized. It illustrates an unusual three-dimensional architecture containing two organic aromatic bicarboxylate ligands with distinct configurations. Moreover, this polymer exhibits strong photoluminescence at room temperature, and the main emission band is at about 390 nm with λ ex  = 337 nm in the solid state at room temperature.A new zinc compound, [Zn3(DPA)2(BDC)] n (1, H2DPA = diphenic acid and H2BDC = benzene-1,4-dicarboxylic acid), has been hydrothermally prepared and characterized. It illustrates an unusual three-dimensional architecture containing two organic aromatic bicarboxylate ligands with distinct configurations. Moreover, this polymer exhibits strong photoluminescence at room temperature, and the main emission band is at about 390 nm with λ ex  = 337 nm in the solid state at room temperature.
Keywords: Metal–organic framework; Fluorescent property; Secondary building unit; Carboxylate ligands; Hydrothermal synthesis;

Magnetic property of a 1D triazacycloalkanes Ni(II) with chiral helical structure complex {[Ni[12]aneN3](μN,S-SCN)(SCN)} n by Gong-Jun Chen; Yan Ouyang; Shi-Ping Yan; Xin Liu; Dai-Zheng Liao; Wen Gu (138-141).
A novel chiral helical triazacycloalkanes 1D complex {[Ni[12]aneN3](μN,S-SCN)2(SCN)} n (1) ([12]aneN3  = 1,5,9-triazacyclododecane) was synthesized and characterized by X-ray single-crystal diffraction, elemental analysis, IR, electronic spectra and magnetic properties.A novel chiral helical triazacycloalkanes 1D complex {[Ni[12]aneN3](μN,S-SCN)(SCN)} n (1) ([12]aneN3  = 1,5,9-triazacyclododecane) was synthesized and characterized by X-ray single-crystal diffraction, elemental analysis, IR, electronic spectra and magnetic properties. The magnetic behaviour reveals a ferromagnetic interaction between Ni(II) ions through μN,S-SCN bridges, 2J  = 5.072 cm−1, g  = 2.159.
Keywords: Macrocyclic ligands; Crystal structure; Magnetic property; Chirality;

Two new chiral MOFs show the first pcu net comprised of six-connected, vertex-shared, bowl-like MNa3 SBUs.In the presence of NaOH, the self-assembly of M(CH3COO)2 and nitrilotriacetate generated two metal–organic polymers, MNa(NTA), (M = Pb(1), Sr(2), NTA3+  = the anion of nitrilotriacetate). The single crystal X-ray diffraction shows that polymers 1 and 2 are isostructural and display the chiral P213 space group with the Flack factor of −0.001(16) for 1 and 0.023(14) for 2. By topology analysis, the complicated architecture of 1 and 2 is simplified to be the 6-connected pcu-type net, which is built on the vertex-shared, bowl-like MNa3 SBUs (pcu  = primitive centered cubic, SBU = secondary building unit).
Keywords: Hydrothermal synthesis; Bowl-like SBUs; pcu-type net; Chiral MOFs;

The 16-electron complexes 1a and 1b react with pyridyl-based ligand bpo and low valent transition metal complex W(CO)3(NC5H5)3 to give two different types of complexes 2a–b and 3a.The mononuclear 16-electron “pseudo-aromatic” dithio-o-carboranylcobalt complex CpCo(S2C2B10H10) (1a) and CpCo(S2C2B10H10) (1b) have been prepared by treatments of CpCo(CO)I2 and CpCo(CO)I2 with the dilithium dithiolato carborane (Li2S2C2B10H10). Both of 1a and 1b react with 2,5-bis(4-pyridyl)-1,3,5-oxadiazole (bpo) to give 2a and 2b. Complex 1a reacts with low valent transition metal complex W(CO)3(py)3 to produce a hetero binuclear Co–W complex 3a. The molecular structures of 1b, 2b and 3a have been determined by X-ray crystallography.
Keywords: Carborane; Dithiolato ligand; Cobalt; Metal–metal bonding; Molecular structures;

A novel metal organic framework [Zn2(BTC)(OH)(I)](BMIM) is synthesized from the ionothermal reaction of Zn(NO3)2 and H3BTC in 1-butyl-3-methylimidazolium iodide, in which the ionic liquid act as both solvents and charge compensating agent. The structure exhibits a three-dimensional framework constructed from unique tetra nuclear building unit [Zn4(OH)2(I)2(CO2)6], which is the first appearance in zinc coordination polymers.A novel coordination polymer, [Zn2(BTC)(OH)(I)](BMIM) (H3BTC = 1,3,5-benzenetricarboxylic acid and BMIM = 1-butyl-3-methylimidazolium), is synthesized from the ionothermal reaction (160 °C, 5 days) of Zn(NO3)2 and H3BTC in 1-butyl-3-methylimidazolium iodide ([BMIM]I) ionic liquid and is structurally characterized. The structure exhibits a three-dimensional framework constructed from tetra nuclear building unit [Zn4(OH)2(I)2(CO2)6], which is the first appearance in zinc coordination polymers. The imidazolium cation [BMIM]+ of the ionic liquid acting as charge compensating agent has strong interactions with the framework. This compound is thermally stable up to ca. 300 °C based on TGA.
Keywords: Ionothermal reaction; Imidazolium iodide; Coordination polymer; Tetra nuclear building unit;

Divalent silver easily transfers the d9 hole to the p orbitals of O in majority of oxo species (such as Ag(OH)2 with the spin density illustrated here) yielding peroxides, as follows from the DFT calculations.The chemistry of divalent silver has so far been limited to fluorine-based anions, such as F, BF 4 - , and SbF 6 - , connections to oxo ligands being scarce. To elucidate the reasons beyond that, we have analyzed the electronic structures of selected hypothetical molecules containing formally Ag(II) in the oxo-ligand environment and we have compared them to AgF2 molecule. Our density functional calculations indicate that the substantial share of spin density resides on the O atoms adjacent to Ag(II) in all oxo species studied; i.e., Ag(II) facilitates the formation (and often subsequent elimination) of peroxo species. Nevertheless, our computations suggest that the chemistry of Ag(II) might be extended beyond the known fluoride, fluorosulfate and triflate connections, to include perchlorate ( ClO 4 - ) , nitrate ( NO 3 - ) , metaphosphate ( PO 3 - ) , perfluoro-t-butoxo species (OC(CF3)3) and perfluorinated ethers, such as CF3–O–CF3.
Keywords: Fluorides; Oxides; Redox reactions; Silver; Density functional theory;

A photoluminescent hexanuclear silver(I) complex exhibiting C–H⋯Ag close interactions by Chun-Sen Liu; Pei-Quan Chen; Ze Chang; Jun-Jie Wang; Li-Fen Yan; Hong-Wei Sun; Xian-He Bu; Zhenyang Lin; Zheng-Ming Li; Stuart R. Batten (159-163).
A photoluminescent hexanuclear discrete AgI complex [Ag6(L 1)6(dmp)2] (1) exhibiting C–H⋯Ag close interactions has been successfully constructed (L 1  = anthracene-9-carboxylate and dmp  = 2,6-dimethylpyridine). The relevant results reveal that the steric bulk of the anthracene ring skeleton of L 1 may play important roles in the formation of the final structure. DFT calculations further supported the existence of the C–H⋯Ag weak interactions in 1. Moreover, the luminescent properties of 1 have also been investigated.The reaction of AgNO3 with bulky anthracene-9-carboxylic acid (HL 1) in the presence of 2,6-dimethylpyridine (dmp) afforded a photoluminescent hexanuclear discrete AgI complex [Ag6(L 1)6(dmp)2] exhibiting C–H⋯Ag interactions whose total interaction energy were further estimated by DFT calculations. The relevant results reveal that the steric bulk of the anthracene ring skeleton of L 1 may play important roles in the formation of the final structure.
Keywords: Photoluminescent Silver(I) complexes; Bulky aromatic skeletons; Crystal structures; Luminescence; C–H⋯Ag close interactions; DFT calculations;

A luminescent Cu(I) complex ligated by 1,3-bis(4-pyridyl)trisulfane generated in situ by the coupling of pyridine-4-thiol by Jian Zhang; Jian-Kai Cheng; Ye-Yan Qin; Zhao-Ji Li; Yuan-Gen Yao (164-166).
A luminescent Cu(I) complex was synthesized via a series of processes under solvothermal condition. It is the first example of a clear transformation from pyridine-4-thiol to a polysulfide compound 1,3-bis(4-pyridyl)trisulfane.A luminescent Cu(I) complex was synthesized via a series of processes under solvothermal condition. It is the first example of a clear transformation from pyridine-4-thiol to a polysulfide compound 1,3-bis(4-pyridyl)trisulfane.
Keywords: Polysulfide; Solvothermal synthesis; Pyridine-4-thiol; Luminescence; Copper(I);

A new cobalodioxime with a tetradentate N4-dioxime ligand, 1D helix of it by unique ‘H-bonding helices’ and its formation of 2D and 3D assembly have been reported.An octahedral cobalodioxime of a new tetradentate dioxime ligand, 3,8-dimethyl-4,7-diazadeca-3,7-diene-2,9-dionedioxime (LH2) and its unprecedented H-bonded self-assembling have been reported. The diamagnetic bioinorganic Cl2Co(LH) (1) unit of zero dimensions assembles to infinite 1D helical strand by novel head-on H-bonding helices. Interstrand facial H-bonding results the 2D helices and interhelices lateral H-bonding (oxime–oxime and Cl–H(CH2)) constructs the 3D framework. The H-bonding effect has been established in solution also and investigated by 1H NMR spectra in DMSO-d 6 and CDCl3 solvents.
Keywords: Cobalodioxime; 3-levels H-bondings; 1D and 2D helices;

The first coordination polymer containing a chiral cyclotriphosphazene ligand by Eric W. Ainscough; Andrew M. Brodie; Ross J. Davidson; Carl A. Otter (171-174).
The first structurally characterised coordination polymer with a chiral cyclotriphosphazene ligand is formed with silver(I).The preparation and the single crystal X-ray structure of a new chiral ligand, 3,3,5,5-tetrapyridyloxy-1,1-{(R)-1,1′-dioxy-2,2′-binapthyl}cyclotriphosphazene (L R ), is described. L R reacts with [Ag(MeCN)4]PF6 to produce the complex {[AgL R ](PF6) · Et2O · 2MeCN} n , which was also characterised by X-ray crystallography. The topology of complex is a 1D coordination polymer that, in the crystalline structure, consists of two different infinite chains arranged in layers that are approximately orthogonal to each another.
Keywords: Cyclotriphosphazene; 1,1′-Dioxy-2,2′-binapthyl; Silver(I); Chiral coordination polymer;

Metal Co(II) and Ni(II) coordination compounds with tetrathiafulvalene carboxylate by Jing Gu; Qin-Yu Zhu; Yong Zhang; Wen Lu; Gai-Yan Niu; Jie Dai (175-178).
Two Co(II) and Ni(II) metal complexes, [Co(H2O)6][Co(L)2(DMF)2] and [Ni(H2O)6][Ni(L)2(DMF)2] were prepared, which are assembled to a 2D sheet by S⋯S contacts with rectangular grid net. The hexaaquometal cations [Co(H2O)6]2+ reside in the cavities of the 2D network and are fixed by O–H⋯O hydrogen bonds.Comparing with the TTF-pyridyl metal complexes, very few compounds have been prepared with TTF-carboxylate ligands. We using 8,9-dimethylthio-2,3-dicarboxylate-tetrathiafulvalene sodium salt as starting material prepared two Co(II) and Ni(II) metal complexes, [Co(H2O)6][Co(L)2(DMF)2] and [Ni(H2O)6][Ni(L)2(DMF)2]. X-ray structure analysis has revealed that the metal ion is coordinated by four carboxylate groups from two ligands in the equatorial plane and two DMF molecules in the apical positions. The molecules are assembled by short S⋯S contacts forming a 2D sheet with rectangular grid net. The hexaaquometal cations [Co(H2O)6]2+ reside in the cavities of the 2D network and are fixed by O–H⋯O hydrogen bonds. Cyclic voltammogram and spectra of the ligand are affected when the metal ion coordinated.
Keywords: Tetrathiafulvalene; Carboxylate; Coordination compound; Crystal structure;

Hexa- and polynuclear copper(II) coordination compounds based on the carbonato bridge: Synthesis, crystal structures and magnetic properties by Sujittra Youngme; Nanthawat Wannarit; Tawun Remsungnen; Narongsak Chaichit; Gerard A. van Albada; Jan Reedijk (179-185).
The crystal structures of polynuclear copper(II) complexes containing the bidentate bpy ligand (bpy = 2,2′-bipyridine) with varied coordination modes of the carbonato bridging ligand, a hexanuclear compound [Cu6(bpy)10(μ-OH)2(μ-CO3)2](CF4SO3)6(DMF)2(H2O)4 (1) and a polymeric compound {[Cu3(bpy)3(μ-OH)2(μ-CO3)2](H2O)6.5} n (2) are described. Compound 1 consists of the di-μ-hydroxido-bis(2,2′-bipyridine)copper(II) groups coordinated with trans-axially at each copper atom by [μ-carbonato-bis(bpy)copper(II)] moieties, forming a hexanuclear copper(II) compound. Each copper(II) ion has a distorted square–pyramidal environment in which three Cu(II) atoms are linked through oxygen atoms of the bridged ligand by the μ321-CO3 coordinated mode. Compound 2 consists of two independent di-μ-hydroxido-bis(2,2′-bipyridine)copper(II) dinuclear units which are connected to the central moiety by two different coordination modes of the carbonate bridging ligands, μ-η11 (anti–anti) and μ-η21-CO3 configurations. Each Cu(II) ion has a distorted square–pyramidal geometry. The repeating units give rise to a one-dimensional chain along b-axis. The lattice structures are stabilized by stacking interaction between pyridine groups of bpy chelated ligands of different units. The spectroscopic properties (IR, Reflectance and EPR spectra) and the magnetic susceptibility data of both compounds are investigated.The crystal structures of polynuclear copper(II) complexes containing the bidentate bpy ligand (bpy = 2,2′-bipyridine) with varied coordination modes of the carbonato bridging ligand, a hexanuclear compound [Cu6(bpy)10(μ-OH)2(μ-CO3)2](CF4SO3)6(DMF)2(H2O)4 (1) and a polymeric compound {[Cu3(bpy)3(μ-OH)2(μ-CO3)2](H2O)6.5} n (2) are described. Compound 1 consists of the di-μ-hydroxido-bis(2,2′-bipyridine)copper(II) groups coordinated with trans-axially at each copper atom by [μ-carbonato-bis(bpy)copper(II)] moieties, forming a hexanuclear copper(II) compound. Each copper(II) ion has a distorted square–pyramidal environment in which three Cu(II) atoms are linked through oxygen atoms of the bridged ligand by the μ321-CO3 coordinated mode. Compound 2 consists of two independent di-μ-hydroxido-bis(2,2′-bipyridine)copper(II) dinuclear units which are connected to the central moiety by two different coordination modes of the carbonate bridging ligands, μ-η11 (anti–anti) and μ-η21-CO3 configurations. Each Cu(II) ion has a distorted square–pyramidal geometry. The repeating units give rise to a one-dimensional chain along b-axis. The lattice structures are stabilized by stacking interaction between pyridine groups of bpy chelated ligands of different units. The spectroscopic properties (IR, Reflectance and EPR spectra) and the magnetic susceptibility data of both compounds are investigated.
Keywords: Carbonate chemistry; Copper(II) complexes; Crystal structure; EPR; Magnetism;

The 3:2 CuCl2/1,4-dihydro-2,3-quinoxalinedione reaction system in DMF in the presence of OHs gives a structurally and magnetically interesting 3D coordination polymer possessing the 2,3-dioxyquinoxalinate(-2) ligand (L2−) and exhibiting the extremely rare (82  · 10)-a [lig (LiGe)] topology. Complex [Cu3L2Cl2(DMF)4] n is the first coordination polymer of any metal with L2− and contains the dianionic ligand in the novel 3.1111 mode.The reaction of 1,4-dihydro-2,3-quinoxalinedione (H2L′) with CuCl2 in the presence of LiOH in DMF has led to the 3D coordination polymer [Cu3L2Cl2(DMF)4] n (1) with an (82  · 10)-a, lig (LiGe), topology, where L2− is 2,3-dioxyquinoxalinate(−2). This compound is the first coordination polymer of any transition metal featuring L2− and contains the ligand in a novel 3.1111 (Harris notation) coordination mode. IR data are discussed in terms of the chemical composition of the polymer and the coordination mode of L2−. Variable-temperature (2–300 K) magnetic susceptibility and variable-field (0–5 T) magnetization studies reveal that L2− propagates weak antiferromagnetic exchange interactions through its “quinoxaline” moiety.
Keywords: Coordination polymers; Copper(II); 1,4-Dihydro-2,3-quinoxalinedione; 2,3-Dioxyquinoxalinate(−2) metal complexes; Magnetic properties;

Solvothermal synthesis a novel hemidirected 2-D (3,3)-net metal-organic framework [Pb(HIDC)] n based on the linkages of left- and right-hand helical chains by Dao-Jun Zhang; Tian-You Song; Jing Shi; Kui-Rong Ma; Ying Wang; Li Wang; Ping Zhang; Yong Fan; Jia-Ning Xu (192-195).
A novel 2-D hemidirected metal-organic framework [Pb(HIDC)] n (1, H3IDC = imidazole-4,5-dicarboxylic acid) has been hydrothermally synthesized and characterized by elemental analyses, IR, TGA, and X-ray single-crystal diffraction. Compound 1 is the first MOF based on Pb(II) and imidazole-4,5-dicarboxylic acid ligand. The 2-D (3,3)-net architecture with a rare (4 · 82) topology is built from alternately arranged left- and right-handed helical chains bridged by HIDC2− ligands.A novel 2-D hemidirected metal-organic framework [Pb(HIDC)] n (1, H3IDC = imidazole-4,5-dicarboxylic acid) has been hydrothermally synthesized and characterized by elemental analyses, IR, TGA, and X-ray single-crystal diffraction. Compound 1 is the first MOF based on Pb(II) and imidazole-4,5-dicarboxylic acid ligand. The 2-D (3,3)-net architecture with a rare (4 · 82) topology is built from alternately arranged left- and right-handed helical chains bridged by HIDC2− ligand.
Keywords: Metal-organic framework; Helical chain; Solvothermal synthesis;

The use of di-2-pyridyl ketone in manganese(II) benzoate chemistry: Two novel Mn 3 II linkage isomers containing the ketone form of the ligand and a neutral Mn 4 II cubane containing the ligand in its gem-diolate(-1) form by Constantinos C. Stoumpos; Ian A. Gass; Constantinos J. Milios; Elena Kefalloniti; Catherine P. Raptopoulou; Aris Terzis; Nikolia Lalioti; Euan K. Brechin; Spyros P. Perlepes (196-202).
The 3:2 Mn(O2CPh)2  · 2H2O/di-2-pyridyl ketone reaction system in MeCN gives two linear Mn 3 II linkage isomers containing the ketone form of the ligand; in the orange isomer the ligand is N,N′-chelating, while in the yellow isomer the ligand is N,O-chelating. The reaction of Mn(O2CPh)2  · 2H2O and di-2-pyridyl ketone in CH2Cl2 yields a Mn 4 II cubane cluster that contains the ligand in its η1113 gem-diolate(-1) form.The use of di-2-pyridyl ketone, (py)2CO, in manganese(II) benzoate chemistry has yielded two Mn 3 II linkage isomers containing the ketone form of the ligand and a neutral Mn 4 II cubane cluster containing the gem-diolate(-1) form of the ligand. The 3:2 Mn(O2CPh)2  · 2H2O/(py)2CO reaction system in MeCN gives a mixture of the orange complex [Mn3(O2CPh)6{(py)2CO-κ2 N,N′}2] (1) and the yellow compound [Mn3(O2CPh)6{(py)2CO-κ2 N,O}2] · 2MeCN (2  · 2MeCN). The known compound [Mn6O2(O2CPh)10(MeCN)4] (3) appears as a by-product when the initial reaction solution, that leads to 1 and 2  · 2MeCN, is allowed to slowly evaporate in the air. The trinuclear molecules adopt a linear structure in both complexes, with one monoatomically bridging η112 and two syn,syn112 carboxylate groups spanning each pair of MnII ions. The terminal MnII ions are each capped by one chelating-N,N′ (py)2CO ligand in 1 and by one chelating-N,O (py)2CO molecule in 2. The 1:1 reaction of Mn(O2CPh)2  · 2H2O and (py)2CO in CH2Cl2 results in the isolation of[Mn4(O2CPh)4{(py)2C(OH)O}4] (4). The tetranuclear molecule has a cubane topology with the MnII ions and the deprotonated oxygen atoms from the (py)2C(OH)O ligands occupying alternate vertices. The IR data are discussed in terms of the nature of the bonding. The magnetic properties of 4 in the 300–5 K range have been modeled with two J values and reveal weak intramolecular antiferromagnetic interactions. The low temperature X-band EPR spectra of 1, 2 and 4 are also discussed.
Keywords: Di-2-pyridyl ketone complexes; EPR spectra; Magnetic properties; Manganese(II) benzoate clusters; Manganese(II) cubanes;

A small and robust Al(III)-chemosensor based on bis-Schiff base N,N′-(1,4-phenylenedimethylidyne)bis-1,4-benzene diamine by Jian-Qiang Wang; Li Huang; Ling Gao; Jian Hua Zhu; Ying Wang; Xiaoxing Fan; Zhigang Zou (203-206).
A sensitive fluorescence chemosensor for Al3+ based on bis-Schiff base PMBA was developed. A naked eye color change form light yellow to colorless with a remarkable fluorescence enhancement of PMBA in the presence of Al3+ is contributed to the formation of new coordinate complex.A sensitive fluorescent chemosensor based on bis-Schiff base N,N′-(1,4-phenylenedimethylidyne) bis-1,4-benzenediamine (PMBA) was developed for detection of Al3+ in aqueous solutions. A naked eye color variation from yellow to colorless is observed along with a remarkable fluorescence enhancement. A good linearity between the fluorescence intensity of the coordinate complex Al3+-PMBA and the concentration of Al3+ (0–30 μM/L), with a detection limit of 2 × 10−6  M was established.
Keywords: Aluminum; Chemosensor; bis-Schiff base; Fluorescence;

A 2D CuII complex containing ferromagnetically coupled 1D chain with threefold bridging ligands by Yin-Feng Han; Tian-Wei Wang; You Song; Zhen Shen; Xiao-Zeng You (207-210).
A new 2D CuII complex [Cu(μ1,1-N3)(tp)(CH3OH)] n (tp = terephthalate) (1) containing one μ-1,1-azido, one (syn–syn) terephthalate and one methanol bridging ligands, has been synthesized and characterized structurally and magnetically. Magnetic measurements indicate that intrachain ferromagnetic and weak interchain antiferromagnetic coupling exist in complex 1.A new 2D CuII complex [Cu(μ1,1-N3)(tp)(CH3OH)] n (tp = terephthalate) (1) has been synthesized and characterized structurally and magnetically. Single-crystal structural analysis shows that complex 1 consists of 1D CuII chains containing threefold bridging ligands, one μ-1,1-azido, one (syn–syn) terephthalate and one methanol, which are bridged via terephthalate anions to afford a 2D network. Magnetic measurements indicate that complex 1 exhibits intrachain ferromagnetic interaction with J  = 63(2) cm−1.
Keywords: CuII complex; Magnetic properties; Azide; Terephthalate;

Synthesis, crystal structure and characterizations of a new 3D porous zinc phosphonate: Zn6[(O3PCH2)2NHC6H11]4  · 6H2O by Jing Li; Lei Meng; Zhen-Gang Sun; Zhong-min Liu; Yan Zhao; Jing Zhang; Yan-Yu Zhu; Xin Lu; Lei Liu; Na Zhang (211-214).
A new porous zinc phosphonate, Zn6[(O3PCH2)2NHC6H11]4  · 6H2O with a 3D open-framework has been synthesized under hydrothermal reaction conditions. The structure of compound 1 features a 3D open-framework built from ZnO4 tetrahedra linked together by bridging phosphonate groups. Each zinc cation is tetrahedrally coordinated by four phosphonate oxygen atoms from four ligands, each of which connects with six zinc atoms, resulting in channel systems of different size.A new 3D porous zinc phosphonate, Zn6(HL)4  · 6H2O 1 (H4L = C6H11N(CH2PO3H2)2) has been synthesized by hydrothermal reaction at 180 °C and structurally characterized by X-ray diffraction as well as by infrared spectroscopy, elemental and thermogravimetric analysis. The structure of compound 1 features a 3D open-framework built from ZnO4 tetrahedra linked together by bridging phosphonate groups. Each zinc cation is tetrahedrally coordinated by four phosphonate oxygen atoms from four ligands, each of which connects with six zinc atoms, resulting in channel systems of different size.
Keywords: Metal phosphonates; Crystal structure; Hydrothermal synthesis; Zinc;

Synthesis of palladium(II) pyridyl acylhydrazone complexes and application to homo- and copolymerization of cyclic olefins by Kenichi Ogata; Atsuo Watanabe; Tomoshige Yunokuchi; Akinori Toyota (215-219).
A series of novel palladium(II) complexes bearing pyridyl acylhydrazone ligand were synthesized by the reaction of PdBr2(NCMe)2 with pyridyl acylhydrazone. These palladium complexes showed the high catalytic activity for polymerization of cyclic olefins such as norbornene (NB) or tetracyclododecene (TD). This paper show the first example for the palladium catalyzed polymerization of tetracyclododecene.A series of new palladium(II)/pyridyl acylhydrazone complexes were synthesized through the reaction of PdBr2(NCMe)2 and pyridyl acylhydrazone. The X-ray crystallographic analysis revealed that the palladium center is coordinated by two bromide atoms and two nitrogen atoms of pyridyl acylhydrazone ligand. This coordination mode of pyridyl acylhydrazone ligand forms a striking contrast to the corresponding nikel(II)/pyridyl acylhydrazone complexes. These new palladium complexes showed high catalytic activity for homopolymerization of cyclic olefins such as norbornene and tetracyclododecene, and for copolymerization of tetracyclododecene with norbornene in the presence of MAO.
Keywords: Palladium complex; Polymerization; Cyclic olefin; Tetracyclododecene; Norbornene;

A novel chiral 3D supramolecular framework based on organooxotin cluster by Shun-Li Li; Guang-Ju Ping; Jie Liu; Jian-Fang Ma; Zhong-Min Su (220-224).
A novel triorganotin compound, namely [(Ph3Sn)3(CO3)(EtOH)3] · (ntb) · Cl · H2O, exhibits the novel chiral 3D supramolecular structure with a (10, 3) topology based on the organooxotin cluster, in which ntb ligand and [(Ph3Sn)3(CO3)(EtOH)3]+ unit act as three-connected nodes and link each other through O–H⋯N bonds.A novel triorganotin compound, namely [(Ph3Sn)3(CO3)(EtOH)3] · (ntb) · Cl · H2O (1), exhibits the novel chiral 3D supramolecular structure with a (10, 3) topology based on the organooxotin cluster, in which ntb ligand and [(Ph3Sn)3(CO3)(EtOH)3]+ unit act as three-connected nodes and link each other through O–H⋯N bonds.
Keywords: Organotin(IV); Cluster; Chiral; Topology;

Solvothermal synthesis, structure and luminescent properties of a new 3D coordination polymer [K2Cd(Htda)2] n (Htda = 1,2,3-triazole-4,5-dicarboxylate) by Guang-Fei Liu; Zhi-Gang Ren; Yang Chen; Dong Liu; Hong-Xi Li; Yong Zhang; Jian-Ping Lang (225-229).
A novel 3D coordination polymer [K2Cd(Htda)2] n (1) (Htda = 1,2,3-triazole-4,5-dicarboxylate) was synthesized by reactions of Cd(OAC)2  · 2H2O H3tda and K2CO3 under the solvothermal conditions. The molecular structure of 1 was characterized by elemental analysis, IR, and X-ray crystallography and its luminescent properties were investigated.A novel cadmium(II)/Htda coordination polymer [K2Cd(Htda)2] n (1) (Htda = 1,2,3-triazole-4,5-dicarboxylate) was prepared through solvothermal methods and structurally characterized. An X-ray analysis reveals that 1 consists of an unusual 3D (4,4,6)-connected network with a (4264)Cd(42638)K(4361082)Htda topology constructed from [ Cd ( Htda ) 2 ] n 2 n - anionic chains and K+ ions via a series of K–O bonding interactions. The luminescent properties of 1 along with the H3tda ligand in the solid state were investigated.
Keywords: Cadmium; Solvothermal synthesis; 1H-1,2,3-Triazole-4,5-dicarboxylic acid; Luminescence; Coordination polymer;